Heat dissipating diluent in fixed bed reactors

ABSTRACT

Incorporating into a fixed bed reactor for an exothermal reaction having a catalyst supported on a support having a thermal conductivity typically less than 30 W/mk within the reaction temperature control limits heat dissipative particles having a thermal conductivity of at least 50 W/mk less than 30 W/mk within the reaction temperature control limits helps control the temperature of the reactor bed.

TECHNICAL FIELD

The present invention relates to the use of a heat dissipating diluentin fixed reactors to seek to reduce the risk of a runaway reaction. Manychemical reactions are exothermic, and particularly treatments ofhydrocarbons in fixed beds. A problem can arise if the rector starts tobecome too hot. As the reactor heats the rate of reaction increasesadding more heat to the reactor further increasing the rate of reaction.In many instances for safety reasons it is necessary to have “killsystems” designed into the reactor to rapidly shut down a reactor.

BACKGROUND ART

U.S. Pat. No. 6,013,741 issued Jan. 11, 2000 to Ohtani et al., assignedto Mitsui teaches the design of a reactor to permit the rapidintroduction of a kill gas into a fluidized bed reactor to rapidly stopa reaction in the event of an equipment failure.

U.S. Pat. No. 8,435,920 issued May 7, 2013 to White et al., assigned toEltron Research & Development, Inc. refers at Col. 1 lines 45 through 66to Lyon which teaches the use of metal oxide catalysts in the partialoxidation of hydrocarbon feeds. The reference does not refer to usinginert metallic dilluents in a reactor bed.

There are a number of United States patents assigned to Petro-TexChemical Corporation issued in the late 1960's that disclose the use ofvarious ferrites in a steam cracker to produce olefins from paraffins.The patents include U.S. Pat. Nos. 3,420,911 and 3,420,912 in the namesof Woskow et al. The patents teach introducing ferrites such as zinc,cadmium, and manganese ferrites (i.e. mixed oxides with iron oxide). Theferrites are not inert and release oxygen to react with the hydrocarbonstream. The ferrites are introduced into a dehydrogenation zone at atemperature from about 250° C. up to about 750° C. at pressures lessthan 100 psi (689.476 kPa) for a time less than 2 seconds, typicallyfrom 0.005 to 0.9 seconds. The reaction appears to take place in thepresence of steam that may tend to shift the equilibrium in the “wrong”direction. Additionally the reaction does not take place in the presenceof a catalyst.

U.S. Pat. No. 2,267,767, issued Dec. 30, 1941 to Thomas, assigned toUniversal Oil teaches the use of non porous metallic substrates assupports for catalysts for the treatment of hydrocarbons. The metallicsubstrates are treated with non aqueous solutions of a metallic alkoxideand an alkyl ortho silicate. The substrate appears to be a component forthe reaction. The metal oxides may be alumina, zirconia, thoria,vanadia, magnesia and other metal oxides which are active in thecracking and or reforming reactions.

U.S. Pat. No. 2,478,194 issued Aug. 9, 1949 assigned to Houdry ProcessCorporation teaches a composite shaped catalyst and support comprising ametallic component such as iron or steel. The metallic component maytake a number of shapes such as an “I” a cross, or even the shape of achild's jack. The catalytic component is then applied to the metallicsupport to form the catalyst. The metallic component provides anoxidation promoter not an inert heat sink.

The fixed bed reactor is a workhorse of the petrochemical and refiningindustry. In commercial reactors the ratio of reactor diameter toeffective particle diameter is at least 50:1 generally greater than500:1. Catalyst supports generally have a low thermal conductivity.Under these conditions there is a low transfer of heat from the interiorof the fixed bed to the reactor wall where heat may be dissipated. Theseconditions may lead to localized hot spots which can be the center for arunaway reaction, particularly for exothermic reactions.

The present invention seeks to provide a fixed bed of catalyst and ametallic diluent having a thermal conductivity of greater than 30 W/mK(watts/meter Kelvin) within the reaction temperature control limits topermit the transfer of heat within the bed and also out of the bed.

DISCLOSURE OF INVENTION

In one embodiment the present invention provides a process forconducting an exothermic reaction in the presence of a fixed bedcomprising supported catalyst the improvement comprising incorporatinginto the bed from 5 to 90 wt. % based on the entire weight of thecatalyst bed of one or more inert non catalytic heat dissipativeparticles having a melting point at least 30° C. above the temperatureupper control limit for the reaction, a particle size within 1 mm to 15mm and a thermal conductivity of greater than 50 W/mK (watts/meterKelvin) within the reaction temperature control limits.

In a further embodiment the particulates are metals, alloys andcompounds having a thermal conductivity of greater than 150 W/mK(watts/meter Kelvin) within the reaction temperature control limits.

In a further embodiment the inert heat dissipative particles comprisesilver, copper, gold, steel, stainless steel, molybdenum and tungsten.

In a further embodiment the reaction involves one or more of cracking,isomerization, oxidative coupling, oxidative dehydrogenation, hydrogentransfer, polymerization, and desulphurization of a hydrocarbon or anyother exothermic reaction.

In a further embodiment the particulates are metallic.

In a further embodiment the particulates have a size from 0.5 mm to 75mm.

In a further embodiment the process is the oxidative coupling of one ormore C₁₋₄ hydrocarbons.

In a further embodiment the process is the oxidative dehydrogenation ofone or more C₂₋₄ hydrocarbons.

In a further embodiment the process is conducted using a mixed feed ofethane and oxygen in a volume ratio from 70:30 to 95:5 at a temperatureupper control limit less than 420° C. at a gas hourly space velocity ofnot less than 280 hr⁻¹ and a pressure from 80 to 1000 kPa (about 0.8 to10 atmospheres).

In a further embodiment the process has a conversion of ethane of notless than 90%.

In a further embodiment t the gas hourly space velocity of the processis not less than 280 hr⁻¹ (preferably at least 1000 hr⁻¹).

In a further embodiment the temperature upper control limit is less than400° C.

In a further embodiment the catalyst has the empirical formulaMo_(g)V_(h)Te_(i)Nb_(j)Pd_(k)O_(l), wherein g, h, i, j, k and l are therelative atomic amounts of the elements Mo, V, Te, Nb, Pd and O,respectively, and when g=1, h ranges from 0.01 to 1.0, i ranges from0.01 to 1.0, j ranges from 0.01 to 1, 0.001<k≤0.10 and l is dependent onthe oxidation state of the other elements.

In a further embodiment the catalyst has the empirical formulaV_(x)Mo_(y)Nb_(z)Te_(m)Me_(n)O_(p)wherein Me is a metal selected from the group consisting of Ta, Ti, W,Hf, Zr, Sb and mixtures thereof; andx is from 0.1 to 3 provided that when Me is absent x is greater than0.5;y is from 0.5 to 1.5;z is from 0.001 to 3;m is from 0.001 to 5;n is from 0 to 2;and p is a number to satisfy the valence state of the mixed oxidecatalyst.

In a further embodiment the crystalline phase of the catalyst has theformula Mo_(1.0)V_(0.22-0.35)Te_(0.10-0.20)Nb_(0.15-0.19)O_(d),preferably Mo_(1.0)V_(0.22-0.33)Te_(0.10-0.16)Nb_(0.15-0.18)O_(d) whered is a number to satisfy the valence of the oxide (as determined byPIXE)

In a further embodiment the crystalline phase of the catalyst the amountof the phase having the formula(TeO)_(0.39)(Mo_(3.52)V_(1.06)Nb_(0.42))O₁₄ is above 75 wt. % asdetermined by XRD

In a further embodiment the crystalline phase of the catalyst the amountof the phase having the formula(TeO)_(0.39)(Mo_(3.52)V_(1.06)Nb_(0.42))O₁₄ is above 85 wt. % asdetermined by XRD.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is a schematic diagram of the fixed bed reactor used to conductthe experiments.

BEST MODE FOR CARRYING OUT THE INVENTION

Numbers Ranges

Other than in the operating examples or where otherwise indicated, allnumbers or expressions referring to quantities of ingredients, reactionconditions, etc. used in the specification and claims are to beunderstood as modified in all instances by the term “about”.Accordingly, unless indicated to the contrary, the numerical parametersset forth in the following specification and attached claims areapproximations that can vary depending upon the properties that thepresent invention desires to obtain. At the very least, and not as anattempt to limit the application of the doctrine of equivalents to thescope of the claims, each numerical parameter should at least beconstrued in light of the number of reported significant digits and byapplying ordinary rounding techniques.

Notwithstanding that the numerical ranges and parameters setting forththe broad scope of the invention are approximations, the numericalvalues set forth in the specific examples are reported as precisely aspossible. Any numerical values, however, inherently contain certainerrors necessarily resulting from the standard deviation found in theirrespective testing measurements.

Also, it should be understood that any numerical range recited herein isintended to include all sub-ranges subsumed therein. For example, arange of “1 to 10” is intended to include all sub-ranges between andincluding the recited minimum value of 1 and the recited maximum valueof 10; that is, having a minimum value equal to or greater than 1 and amaximum value of equal to or less than 10. Because the disclosednumerical ranges are continuous, they include every value between theminimum and maximum values. Unless expressly indicated otherwise, thevarious numerical ranges specified in this application areapproximations.

All compositional ranges expressed herein are limited in total to and donot exceed 100 percent (volume percent or weight percent) in practice.Where multiple components can be present in a composition, the sum ofthe maximum amounts of each component can exceed 100 percent, with theunderstanding that, and as those skilled in the art readily understand,that the amounts of the components actually used will conform to themaximum of 100 percent.

The Catalyst

The present invention is suitable for use with any fixed bed reactor inwhich there is a desire to have a better control over the heat flowwithin the fixed bed and also the transfer of heat into or out of thebed. Since the inert non catalytic heat dissipative particles present inthe bed have a thermal conductivity of greater than 50, in someembodiments 100, in further embodiments 150, still further embodiments200, W/mK (watts/meter Kelvin) within the reaction temperature controllimits, the inert non catalytic heat dissipative particles may transferheat directly to the walls of the reactor improving the coolinghomogeneity (or heating if the wall are heated) and reduction of hotspots in the fixed bed.

The reactions may comprise one or more of oxidative cracking,isomerization, oxidative coupling, oxidative dehydrogenation, hydrogentransfer, polymerization, and desulphurization of a hydrocarbon or anyother exothermic reaction. In some embodiments the reaction is oxidativedehydrogenation of a C₂₋₄ alkane or the oxidative coupling of a C₁₋₄alkane. These last two reactions are of concern as the feed comprises ahydrocarbon and oxygen. If the ratio of oxygen to hydrocarbon exceedsthe lower flammability (explosive) limit and the reaction temperature ofthe bed exceeds the ignition temperature of the mixture there is acertainty of an undesired outcome.

In some methods of carrying out such reactions the reactant stream isdiluted with steam or an inert gas such as nitrogen to keep the reactivemixture below the lower flammability (explosive) limit. This type ofapproach tends to reduce the per pass conversion of the reactants andproduct stream needs to be separated, typically using some type of unitlike a C₂ splitter which is energy intensive and greenhouse gasproducing.

Another approach is to operate such reactions above the lowerflammability (explosive) limit but at a temperature below theauto-ignition temperature of the feed. In such a method of operation itis critical to have a uniform temperature within the bed (i.e. no hotspots) and to have a good control over the removal of heat from thefixed bed.

There are a number of catalyst which may be used for oxidativedehydrogenation.

In some embodiments the catalyst may have the compositionMo_(a)V_(b)Nb_(c)Sb_(d)X_(e). X is nothing or Li, Sc, Na, Be, Mg, Ca,Sr, Ba, Ti, Zr, Hf, Y, Ta, Cr, Fe, Co, Ni, Ce, La, Zn, Cd, Hg, Al, Tl,Pb, As, Bi, Te, U, Mn and/or W; a is 0.5-0.9, b is 0.1-0.4, c is0.001-0.2, d is 0.001-0.1, e is 0.001-0.1 when X is an element.

In some embodiments the catalyst has the formula:Mo_(a)V_(v)Ta_(x)Te_(y)O_(z)wherein, a is 1.0, v is about 0.01 to about 1.0, x is about 0.01 toabout 1.0, and y is about 0.01 to about 1.0, and z is the number ofoxygen atoms necessary to render the catalyst electronically neutral.The catalyst may be supported on typical supports including poroussilicon dioxide, ignited silicon dioxide, kieselgur, silica gel, porousor nonporous aluminum oxide, titanium dioxide, zirconium dioxide,thorium dioxide, lanthanum oxide, magnesium oxide, calcium oxide, bariumoxide, tin oxide, cerium dioxide, zinc oxide, boron oxide, boronnitride, boron carbide, boron phosphate, zirconium phosphate, aluminumsilicate, silicon nitride or silicon carbide, but also glass metal-oxideor metal networks. In some embodiments titanium oxide.

In some embodiments the catalyst may have the formula:V_(x)Mo_(y)Nb_(z)Te_(m)Me_(n)O_(p)wherein Me is a metal selected from the group consisting of Ta, Ti, W,Hf, Zr, Sb and mixtures thereof; andx is from 0.1 to 3 provided that when Me is absent x is greater than0.5;y is from 0.5 to 1.5;z is from 0.001 to 3;m is from 0.001 to 5;n is from 0 to 2;and p is a number to satisfy the valence state of the mixed oxidecatalyst.

In some examples, the catalyst may have the empirical formula (measuredby PIXE):Mo_(1.0)V_(0.22-0.33)Te_(0.10-0.16)Nb_(0.15-0.18)O_(d)wherein d is a number to satisfy the valence of the oxide.

In some embodiments, the catalyst may have the empirical formulaMo_(g)V_(h)Te_(i)Nb_(j)Pd_(k)O_(l), wherein g, h, i, j, k and l are therelative atomic amounts of the elements Mo, V, Te, Nb, Pd and O,respectively, and when g=1, h ranges from 0.01 to 1.0, i ranges from0.01 to 1.0, j ranges from 0.01 to 1, 0.001<k≤0.10 and l is dependent onthe oxidation state of the other elements. The addition of small amountsof Pd into the catalyst provides an increase in activity whilemaintaining high selectivity for ethylene.

In an embodiment of this Pd containing catalyst, the relative atomicamount of the element vanadium, indicated by subscript h, ranges from0.1 to 0.5. In another embodiment of the catalyst, h ranges from 0.2 to0.4. In a further embodiment of then catalyst h ranges from 0.25 to0.35.

In an embodiment of this Pd containing catalyst, the relative atomicamount of the element tellerium, indicated by subscript i, ranges 0.05to 0.4. In another embodiment of the catalyst, i ranges from 0.08 to0.3. In a further embodiment of the catalyst, i ranges from 0.10 to0.25.

In an embodiment of this Pd containing catalyst, the relative atomicamount of the element niobium, indicated by subscript j, ranges from0.05 to 0.4. In another embodiment of the catalyst, j ranges from 0.08to 0.3. In a further embodiment of the catalyst, j ranges from 0.10 to0.25.

Hydrothermal synthesis for preparation of mixed metal oxide catalysts isknown in the art, its advantages over conventional preparation methodssuch as solid-state reaction and dry-up are covered in Watanabe, et al.,“New Synthesis Route For Mo—V—Nb—Te Mixed Metal Oxides For PropaneAmmoxidation,” Applied Catalysis A: General, 194-195, pp. 479-485(2000).

Generally a hydrothermal synthesis step is used for preparation of thecatalyst prior to addition of the Pd compound. Compounds containingelements Mo, V, Nb, and Te and a solvent are mixed to form a firstadmixture. The first admixture is then heated in a closed vessel forfrom 24 to 240 hours. One useful solvent for the hydrothermal synthesisof the first admixture is water. Any water suitable for use in chemicalsyntheses can be utilized, and includes, without limitation, distilledwater, de-ionized, water. The amount of solvent used is not critical forthe present invention.

Preparation of the admixture is not limited to addition of all compoundsof Mo, V, Nb, and Te at the same time prior to heat treatment in a firstclosed vessel. For example, the Mo and Te compounds may be added first,followed by the V compound and eventually the Nb compound. For a furtherexample, the process may be reversed in that the Te and Nb compounds arecombined followed by addition of a mixture of the Mo and V compounds.Other sequences of addition would be apparent to a person skilled in theart. Sequence and timing of addition is not limited by these examples.

In an embodiment of the invention, the first admixture is heated at atemperature of from 100° C. to 200° C. In another embodiment of theinvention, the first admixture is heated at a temperature from 130° C.to 190° C. In a further embodiment of the invention, the first admixtureis heated at a temperature from 160° C. to 185° C.

Following hydrothermal synthesis of the first four components of thecatalyst the first insoluble material is recovered from the first closedvessel. At this point, the first insoluble material may be dried priorto a first calcining in order to remove any residual solvent. Any methodknown in the art may be used for optional drying of the first insolublematerial, including, but not limited to, air drying, vacuum drying,freeze drying, and oven drying.

In a further embodiment of the invention the first insoluble materialmay be subjected to peroxide washing prior to optional drying and priorto a first calcining. The peroxide washing treatment may take place atatmospheric pressure and room temperature (e.g. from 15° C. to 30° C.)to about 80° C., in some instances from 35° C. to 75° C. in otherinstances from 40° C. to 65° C. and the peroxide has a concentrationfrom 10 to 30 wt. %, in some instances form 15 to 25 wt. %, and a timefrom 1 to 10 hours, in some cases from 2 to 8 hours, in other cases from4 to 6 hours.

The first insoluble material is treated with the equivalent of from 1.3to 3.5 mls of a 30 wt. % solution of H₂O₂ per gram of precursor. Thetreatment should be in a slurry (e.g. the precursor is at leastpartially suspended) to provide an even distribution of H₂O₂ and tocontrol the temperature rise. For post calciniation treatment with H₂O₂there is a delayed violent reaction with H₂O₂. The process of thepresent invention is an instantaneous reaction which is more controlledand safer.

Methods for calcination are well known in the art. The first calciningof the first insoluble material is conducted in a second closed vesselwith an inert atmosphere. The second closed vessel for the calcinationmay be a quartz tube. The inert atmosphere may include any material thatdoes not interact or react with the first insoluble material. Examplesinclude, without limitation, nitrogen, argon, xenon, helium or mixturesthereof. The preferred embodiment of the present invention comprises aninert atmosphere comprising gaseous nitrogen.

Calcination methods for preparation of mixed metal oxide catalysts varyin the art. Variables include the time, temperature range, the speed ofheating, use of multiple temperature stages, and the use of an oxidizingor inert atmosphere. For the present invention the speed of heating isnot critical and may range from between 0.1° C./minute to around 10°C./minute. Also, the inert gas may be present statically or may bepassed over the catalyst at flow rates where the loss of catalyst isminimized, i.e. carryover out of bed.

In an embodiment of the invention the time for the first calciningranges from 1 hour to 24 hours. In another embodiment of the inventionthe time for the first calcining ranges from 3 hours to 15 hours. In thepreferred embodiment of the invention the time for the first calciningranges from 4 hours to 12 hours.

In an embodiment of the invention the first calcining takes place in aninert atmosphere at a temperature from 500° C. to 700° C. In anotherembodiment of the invention the first calcining takes place in an inertatmosphere at a temperature from 550° C. to 650° C. In the preferredembodiment of the invention the first calcining takes place in an inertatmosphere at a temperature of from 580° C. to 620° C. The resultingcalcined product is suitable as an oxidative dehydrogenation catalyst.

In some embodiments following the first calcining, the first calciningproduct is mixed with a Pd component to form a second admixture. Forthese aspects of the invention the addition of a Pd component to thecatalyst is only effective in increasing the activity of the catalyst,without significantly decreasing the selectivity, depending on themethod for addition and the nature of the Pd compound used. The additionof the Pd compound must be performed following the first calcining ofthe first insoluble material containing the four components Mo, V, Te,and Nb. In an embodiment of the invention the Pd compound, in the formof an aqueous solution, is added dropwise to the first calcining productuntil saturation and the mixture forms a paste. In another embodiment ofthe invention, the Pd component and the first calcining product aremixed in an aqueous solution to form a slurry. In an embodiment of theinvention the aqueous solution is water. Any water suitable for use inchemical syntheses can be utilized, and includes, without limitation,distilled water and de-ionized water. The amount of solvent used is notcritical for the present invention.

The amount of Pd component added, either in dropwise fashion or in aslurry, will correspond roughly with 0.044 mmol_(Pd)/g_(ODH catalyst) toyield a final relative atomic amount of Pd, represented by the subscripte in the formula Mo_(a)V_(b)Te_(c)Nb_(d)Pd_(e)O_(f), between 0.001 and0.1.

The nature of the Pd compound used must be free of halogens. One usefulPd component is tetra-amine Pd nitrate, chemically represented by theformula [(NH₃)₄Pd](NO₃)₂.

Before the second calcining the second admixture, the product may bedried using any method known in the art, including, but not limited to,air drying, vacuum drying, freeze drying, and oven drying.

The second calcining is performed under conditions and follows the samelimitations as those applicable to the first calcining. The resultingsecond insoluble material is retrieved from the second closed vessel andcan be used directly as a catalyst for ODH, using conditions where theonly atmospheric components exposed to the catalyst are oxygen andethane. The ratios of oxygen and ethane and the temperature used for theODH process are such that the upper explosive limit is not triggered.The ability to perform ODH using this catalyst whereby there is nodilution of the reactants with nitrogen or other inert gas or waterconfers a commercial advantage as costly downstream processes for theremoval of excess oxygen or any unwanted byproducts are not required orare limited in nature.

In some embodiments the catalyst may have the formula:Mo_(a)V_(b)Nb_(c)Te_(e)O_(d)wherein:a is from 0.75 to 1.25, preferably from 0.90 to 1.10;b is from 0.1 to 0.5, preferably from 0.25 to 0.4;c is from 0.1 to 0.5, preferably from 0.1 to 0.35;e is from 0.1 to 0.35 preferably from 0.1 to 0.3; andd is a number to satisfy the valence state of the mixed oxide catalyst.

The above MoVNbTeMeO type catalysts are heterogeneous. They have anamorphous phase and a crystalline phase. The structure and content ofthe crystalline phase may be influenced by treatment of the catalystwith hydrogen peroxide prior to final calcining (i.e. catalyst precursortreatment). Following such a treatment the crystalline phase of thecatalyst has the formula:Mo_(1.0)V_(0.25-0.35)Te_(0.10-0.20)Nb_(0.15-0.19)O_(d)where d is a number to satisfy the valence of the oxide. In someembodiments at least 75 wt. % of the crystalline phase has the precedingformula as determined by XRD. In other embodiments at least 85 wt. % ofthe crystalline phase has the preceding formula as determined by XRD.The Support

The support for the catalyst for the fixed bed may be ceramic precursorformed from oxides, dioxides, nitrides, carbides selected from the groupconsisting of silicon dioxide, fused silicon dioxide, aluminum oxide,titanium dioxide, zirconium dioxide, thorium dioxide, lanthanum oxide,magnesium oxide, calcium oxide, barium oxide, tin oxide, cerium dioxide,zinc oxide, boron oxide, boron carbide, yttrium oxide, aluminumsilicate, silicon nitride, silicon carbide and mixtures thereof.Typically the thermal conductivity of the support is less than 50 W/mk,preferably less than 30 W/mk within the reaction temperature controllimits.

In one embodiment the support for the fixed bed may have a low surfacearea less than 20 m²/g, alternatively, less than 15 m²/g, alternatively,less than 3.0 m²/g for the oxidative dehydrogenation catalyst. Suchsupport may be prepared by compression molding. At higher pressures theinterstices within the ceramic precursor being compressed collapse.Depending on the pressure exerted on the support precursor the surfacearea of the support may be from about 20 to 10 m²/g.

The low surface area support could be of any conventional shape such asspheres, rings, saddles, etc.

It is important that the support be dried prior to use (i.e. beforeadding catalyst). Generally, the support may be heated at a temperatureof at least 200° C. for up to 24 hours, typically at a temperature from500° C. to 800° C. for about 2 to 20 hours, preferably 4 to 10 hours.The resulting support will be free of adsorbed water and should have asurface hydroxyl content from about 0.1 to 5 mmol/g of support,preferably from 0.5 to 3 mmol/g.

The amount of the hydroxyl groups on silica may be determined accordingto the method disclosed by J. B. Peri and A. L. Hensley, Jr., in J.Phys. Chem., 72 (8), 2926, 1968, the entire contents of which areincorporated herein by reference.

The dried support for the fixed bed catalyst may then be compressed intothe required shape by compression molding. Depending on the particlesize of the support, it may be combined with an inert binder to hold theshape of the compressed part.

Loadings

Typically the catalyst loading on the support for the fixed bed catalystprovides from 1 to 30 weight % typically from 5 to 20 weight %,preferably from 8 to 15 weight % of said catalyst and from 99 to 70weight %, typically from 80 to 95 weight %, preferably from 85 to 92weight %, respectively, of said support. The heat dissipative particlesare different from the support.

The catalyst may be added to the support in any number of ways. Forexample the catalyst could be deposited from an aqueous slurry onto oneof the surfaces of the low surface area support by impregnation,wash-coating, brushing or spraying. The catalyst could also beco-precipitated from a slurry with the ceramic precursor (e.g. alumina)to form the low surface area supported catalyst.

The Heat Dissipative Particles for the Fixed Bed

The heat dissipative particles for the fixed bed comprises one or morenon catalytic inert particulates having a melting point at least 30, insome embodiments at least 250, in further embodiments at least 500° C.above the temperature upper control limit for the reaction, a particlesize in range of 0.5 to 75 mm, in some embodiments 0.5 to 15, in furtherembodiments in range of 0.5 to 8, desirably in the range of 0.5 to 5 mmand a thermal conductivity of greater than 30 W/mK (watts/meter Kelvin)within the reaction temperature control limits. In some embodiments theparticulates are metals alloys and compounds having a thermalconductivity of greater than 50 W/mK (watts/meter Kelvin) within thereaction temperature control limits. Some suitable metals includesilver, copper, gold, aluminum, steel, stainless steel, molybdenum, andtungsten.

The heat dissipative particles may have a particle size typically fromabout 1 to 15 mm. In some embodiments the particle size may be fromabout 1 mm to about 8 mm. The heat dissipative particles may be added tothe fixed bed in an amount from 5 to 95 wt. %, in some embodiments 30 to70 wt. %, in other embodiments 45 to 60 wt. % based on the entire weightof the fixed bed.

The Processes

The present invention may be used with any fixed bed exothermicreaction. In some embodiments the fixed bed reactor is a tubular reactorand in further embodiment the fixed bed reactor comprises of multipletubes inside a shell (e.g. a shell and tube heat exchanger typeconstruction). In a further embodiment the fixed bed reactor maycomprise a number of shells in series and/or parallel. The reactions mayinvolve one or more of cracking, isomerization, dehydrogenationincluding oxidative dehydrogenation, hydrogen transfer includingoxidative coupling and desulphurization of a hydrocarbon.

Typically these reactions are conducted at temperatures from about 200°C. up to about 850° C. at pressures from about 80 to 21,000 kPa (about12 to 3000 psi) in the presence of a catalyst. The hydrocarbon streammay contain a wide range of compounds including C₁₋₂₀ aliphatic, oraromatic hydrocarbons.

In some embodiments, the reactions are the oxidative coupling ofaliphatic hydrocarbons, typically C₁₋₄ aliphatic hydrocarbonsparticularly methane and the oxidative dehydrogenation of C₂₋₄ aliphatichydrocarbons. Such reactions may be conducted using a mixed feed ofhydrocarbon, in some embodiments methane or ethane and oxygen in avolume ratio from 70:30 to 95:5 at a temperature less than 420° C. at agas hourly space velocity of not less than 280 hr⁻¹, in some embodimentsnot less than 1000 hr⁻¹, in some embodiments not less than 2000 hr⁻¹ anda pressure from 80 to 1000 kPa (0.8 to 1.2 atmospheres). Typically, theprocess may have an overall conversion of from about 50 to about a 100%,typically from about 75 to 98% and a selectivity to ethylene of not lessthan 90%, in some instances not less than 95%, in further embodimentsnot less than 98%. In some cases, the temperature upper control limit isless than about 400° C., in some embodiments less than 385° C.

The resulting product stream is treated to separate ethylene from therest of the product stream which may also contain co-products such asacetic acid, and un-reacted feed which is recycled back to the reactor.

Additionally, the product stream should have a low content of carbondioxide, and carbon monoxide, and acetic acid, generally cumulatively ina range of less than 10, preferably less than 2 wt. %.

There are up to four competing reactions for oxidative dehydrogenation.C₂H₆+0.5O₂

C₂H₄+H₂O (ΔH1=−105 kJ/Mole C2H6)  Reaction 1C₂H₆+2.5O₂

2CO+3H₂O (ΔH2=−862 kJ/Mole C2H6)  Reaction 2C₂H₆+3.5O₂

2CO₂+3H₂O (ΔH3=−1430 kJ/Mole C2H6)  Reaction 3C₂H₆+1.5O₂

C₂H₂O₂+H₂O (ΔH4=−591 kJ/Mole C2H6)  Reaction 4

From a temperature/heat control point of view, if a catalystpreferentially leads to reaction 1, there is a lower potential for athermal runaway.

The feed and by products may need to be separated from the productstream. Some processes may use so called dilute ethylene streams. Forexample, if the product stream does not contain too much ethane, forexample less than about 15 vol. % the stream may be fed directly withoutfurther purification to a polymerization reactor such as a gas phase,slurry or solution reactor.

The most common separation technique would be to use a cryogenic C2splitter. Other known ethylene/ethane separation techniques could alsobe used including adsorption (oil, ionic liquids and zeolite).

The present invention will now be illustrated by the following nonlimiting examples.

In the examples, the catalysts were prepared by a hydrothermal processas described above.

The catalyst had the empirical formula:(Mo_(1.00)V_(0.36)Te_(0.12)Nb_(0.12))O_(4.57) as determined by XRD.

For the comparative example, the catalyst was not treated with hydrogenperoxide. For example 1, the sample comprise a mixture of five catalystsamples treated with per oxide. The catalyst for the comparative examplehas a slightly higher propensity to oxidize feed to CO₂.

In the examples, the fixed bed reactor unit used is schematically shownin FIG. 1. The reactor was a fixed bed stainless steel tube reactorhaving a 2 mm (¾″) outer diameter and a length of 117 cm (46 inches).The reactor is in an electrical furnace sealed with ceramic insulatingmaterial. There are 7 thermocouples in the reactor indicated at numbers1 through 7. Thermocouples are used to monitor the temperature in thatzone of the reactor. Thermocouples 3 and 4 are also used to control theheating of the reactor bed. The feed flows from the top to the bottom ofthe reactor. At the inlet there is a ceramic cup 8 to prevent air draftsin the reactor. Below the ceramic cup is a layer of quartz wool 9. Belowthe layer of quartz wool is a layer of catalytically inert quartzpowder. Below the quarts powder is the fixed bed 10 comprising catalystand diluent. Below the fixed bed is a layer of quartz powder 11, a layerof quartz wool 12 and a ceramic cup 13. At the exit of the bed was a gasanalyzer to determine the composition of the product stream. The fixedbed comprised 28.83 g of catalyst and 3.85 g of diluent (32.86 g totalweight % of diluent 11.7 wt. % of total bed). The GHSV was 2685 hr⁻¹ andthe pressure was ambient.

For the examples, the bed temperature was taken as an average of thetemperatures from thermocouples 2, 3 and 4. The feed stream was assumedto have the same temperature as the bed. A stoichiometric reactor blockwas run using the above temperature conditions using Aspen Plussimulation to calculate the overall heat release of the reactions.

Comparative Example

The heat dissipative particles in this example were quartz particleshaving a mean particle size of 568 micrometers. The reaction temperature(bed temperature) increased to 355° C. and then there was a thermalreaction run away.

The overall conversion to ethylene was 19% and the selectivity toethylene was 93%. The calculated heat duty of the reactions wascalculated to be a heat release of −26.28 kJ/hr. At this time there wasa rapid drop in oxygen content in the product stream and a fast thermalreaction runaway began. The reaction was quenched with nitrogen.

Example 1

The heat dissipative particles were 316 Stainless Steel particles havinga mean particle size of 568 micrometers. The weight % of diluent was thesame as for example 1. As the steel is denser than quartz this resultedin a lower volume % of diluent in the bed. These conditions werebelieved to tend toward a thermal runaway. The reactor was operated tomaintain an overall conversion of 19% with a selectivity to ethylene of89%. The calculated overall heat of reaction was −31.13 kJ/hr. Thetemperature of the bed rose to 372° C. No runaway reaction was observed.The stainless steel diluent permitted a better release of heat throughthe reactor walls to control the reaction.

Example 1 shows the bed temperature did not rise above 372° C. while inthe comparative example the bed temperature approached 355° followed bya thermal reaction run away. Example 1 shows dissipation in the heat ofreaction.

INDUSTRIAL APPLICABILITY

The present invention helps to control/dissipate the heat generated fromthe oxidative dehydrogenation reaction.

The invention claimed is:
 1. A process for conducting an oxidativedehydrogenation comprising: providing a mixed feed of ethane and oxygenin a volume ratio from 70:30 to 95:5; and conducting oxidativedehydrogenation of the mixed feed at a temperature less than 400° C. ata gas hourly space velocity of not less than 280 hr⁻¹, at a pressurefrom 0.8 to 102 atmospheres (80 to 1000 kPa), a conversion of ethane notless than 90%, and in the presence of a fixed bed comprising mixed metaloxide catalyst having a crystalline phase of the formula:Mo_(1.0)V_(0.25-0.35)Te_(0.10-0.20)Nb_(0.15-0.19)O_(d) where d is anumber to satisfy the valence of the oxide; wherein said mixed oxidecatalyst is supported on one or more of porous silicon dioxide, ignitedsilicon dioxide, kieselgur, silica gel, porous or nonporous aluminumoxide, titanium dioxide, zirconium dioxide, thorium dioxide, lanthanumoxide, magnesium oxide, calcium oxide, barium oxide, tin oxide, ceriumdioxide, zinc oxide, boron oxide, boron nitride, boron carbide, boronphosphate, zirconium phosphate, aluminum silicate, silicon nitride orsilicon carbide; wherein said fixed bed further comprises one or moreinert non catalytic heat dissipative particles comprising silver,copper, gold, steel, stainless steel, molybdenum, and tungsten in anamount from 5 to 90 wt. %, based on the weight of the fixed bed; andwherein, said particles have a melting point at least 30° C. above atemperature upper control limit of said oxidative dehydrogenation, aparticle size from 0.5 mm to 5 mm and a thermal conductivity of greaterthan 150 W/mK (watts/meter Kelvin) within the reaction temperaturecontrol limits.
 2. A process for conducting an oxidative dehydrogenationcomprising: providing a mixed feed of ethane and oxygen in a volumeratio from 70:30 to 95:5; and conducting oxidative dehydrogenation ofthe mixed feed at a temperature less than 400° C., at a gas hourly spacevelocity of not less than 280 hr⁻¹, at a pressure from 0.8 to 102atmospheres (80 to 1000 kPa), a conversion of ethane not less than 90%,and in the presence of a fixed bed comprising a mixed metal oxidecatalyst; wherein the fixed bed mixed metal oxide catalyst has acrystalline phase of the formula:Mo_(1.0)V_(0.25-0.35)Te_(0.10-0.20)Nb_(0.15-0.19)O_(d) where d is anumber to satisfy the valence of the oxide; wherein in a crystallinephase of said mixed metal oxide catalyst the amount of a crystallinephase having the formula(TeO)_(0.39)(Mo_(3.52)V_(1.06)Nb_(0.42))O₁₄ is above 75 wt. % asdetermined by XRD; wherein said mixed oxide catalyst is supported on oneor more of porous silicon dioxide, ignited silicon dioxide, kieselgur,silica gel, porous or nonporous aluminum oxide, titanium dioxide,zirconium dioxide, thorium dioxide, lanthanum oxide, magnesium oxide,calcium oxide, barium oxide, tin oxide, cerium dioxide, zinc oxide,boron oxide, boron nitride, boron carbide, boron phosphate, zirconiumphosphate, aluminum silicate, silicon nitride or silicon carbide;wherein said fixed bed further comprises one or more inert non catalyticheat dissipative particles comprising silver, copper, gold, steel,stainless steel, molybdenum, and tungsten in an amount from 5 to 90 wt.%, based on the weight of the fixed bed; and wherein, said particleshave a melting point at least 30° C. above a temperature upper controllimit of said oxidative dehydrogenation, a particle size from 0.5 mm to5 mm and a thermal conductivity of greater than 150 W/mK (watts/meterKelvin) within the reaction temperature control limits.
 3. A process forconducting an oxidative dehydrogenation comprising: providing a mixedfeed of ethane and oxygen in a volume ratio from 70:30 to 95:5; andconducting oxidative dehydrogenation of the mixed feed at a temperatureless than 400° C. at a gas hourly space velocity of not less than 280hr⁻¹, at a pressure from 0.8 to 102 atmospheres (80 to 1000 kPa), aconversion of ethane not less than 90%, and in the presence of a fixedbed comprising a mixed metal oxide catalyst; wherein the fixed bed mixedmetal oxide catalyst has a crystalline phase of the formula:Mo_(1.0)V_(0.25-0.35)Te_(0.10-0.20)Nb_(0.15-0.19)O_(d) where d is anumber to satisfy the valence of the oxide; wherein in the crystallinephase of the catalyst the amount of the said crystalline phase havingthe formula(TeO)_(0.39)(Mo_(3.52)V_(1.06)Nb_(0.42))O₁₄ is above 85 wt. % asdetermined by XRD; wherein said mixed oxide catalyst is supported on oneor more of porous silicon dioxide, ignited silicon dioxide, kieselgur,silica gel, porous or nonporous aluminum oxide, titanium dioxide,zirconium dioxide, thorium dioxide, lanthanum oxide, magnesium oxide,calcium oxide, barium oxide, tin oxide, cerium dioxide, zinc oxide,boron oxide, boron nitride, boron carbide, boron phosphate, zirconiumphosphate, aluminum silicate, silicon nitride or silicon carbide;wherein said fixed bed further comprises one or more inert non catalyticheat dissipative particles comprising silver, copper, gold, steel,stainless steel, molybdenum, and tungsten in an amount from 5 to 90 wt.%, based on the weight of the fixed bed; and wherein, said particleshave a melting point at least 30° C. above a temperature upper controllimit of said oxidative dehydrogenation, a particle size from 0.5 mm to5 mm and a thermal conductivity of greater than 150 W/mK (watts/meterKelvin) within the reaction temperature control limits.